EP2108356B1 - Conditioning agent for the etching of enamel lesions - Google Patents
Conditioning agent for the etching of enamel lesions Download PDFInfo
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- EP2108356B1 EP2108356B1 EP08007195.4A EP08007195A EP2108356B1 EP 2108356 B1 EP2108356 B1 EP 2108356B1 EP 08007195 A EP08007195 A EP 08007195A EP 2108356 B1 EP2108356 B1 EP 2108356B1
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- acrylate
- methacrylate
- dimethacrylate
- kit according
- acid
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Definitions
- the invention relates to a kit for the infiltration of enamel lesions containing a composition for use as a conditioner for the etching of enamel lesions.
- Caries is a widespread lifestyle disease. Any cavitation-related caries disease begins with demineralization of the enamel and is called initial enamel caries at this stage. At this stage, the caries is initially not visible or only as a so-called white tooth enamel lesion, but leads to a porous area of the tooth below the surface.
- Such a enamel lesion can basically be re-mineralized or infiltrated with a synthetic resin ( WO 2007/131725 A1 ).
- a synthetic resin WO 2007/131725 A1
- these pseudointakten surface layers by an etchant pretreatment, so that after this conditioning the infiltrant can penetrate better into the lesion.
- the invention has for its object to provide an effective and well storable and applicable conditioning agent for the etching of enamel lesions.
- the acid having a pKa of 2 or less may be an inorganic or organic acid, mixtures of several acids are also possible.
- the first stage of dissociation from the acidic state of the composition must have a pKa of 2 or less.
- Preferred upper limits for the pKs value are 1.5 and 1.
- the protic solvent may in particular be alcohols or water or mixtures thereof. According to the invention it is provided that the acid and / or the complete composition at 20 ° C have a saturation vapor pressure of 120 mbar or less.
- the saturation vapor pressure is the pressure of the gaseous phase of a substance when the liquid and gas phases are in equilibrium.
- the partial vapor pressure of only the acid in the composition is preferably considered, and then the vapor pressure of the solvent can be disregarded.
- the invention has recognized that in the prior art ( WO 2007/131725 A1 ) used as a conditioning agent hydrochloric acid has a number of disadvantages.
- hydrochloric acid In order to be sufficiently effective as a conditioner, an approximately 15% hydrochloric acid must be used.
- HCl has a considerable vapor pressure in highly concentrated aqueous solutions, so that it escapes in gaseous form from the aqueous hydrochloric acid solution.
- Corresponding hydrochloric acid solutions are therefore less storage-stable;
- because of the high aggressiveness of the gaseous HCl high demands are placed on the resistance of the packaging of the conditioning agent.
- escaping gaseous HCl in use can damage biological tissues such as the gums.
- the invention has recognized that the acids defined in more detail in the claim with a certain minimum value of the acid strength can effectively erode the remineralized surface layers of natural enamel lesions and thus prepare for the penetration of an infiltrant.
- Such pseudointact surface layers of a natural enamel lesion are typically 10 to 40 microns thick and are largely completely penetrated by a composition of the invention in manageable application times (for example, about 90 to 120 s) and completely removed.
- the low saturation vapor pressure provided according to the invention ensures that-unlike the use of hydrochloric acid-there is no escape of aggressive acid constituents during storage or use of the composition according to the invention.
- Suitable acids are, for example, fluorosulfonic acid, organic sulfonic acids, such as, for example, trifluoromethanesulfonic acid, methanesulfonic acid, toluenesulfonic acid, sulfamic acid, benzenesulfonic acid, perchloric acid, sulfuric acid, nitric acid, trichloroacetic acid, trifluoroacetic acid, picric acid or semiqua decarboxylic acid.
- Preferred acids are methanesulfonic acid and p-toluenesulfonic acid.
- Preferred lower limits for the acidity in the conditioning agent are 7% by weight, 10% by weight, 11% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 40% by weight and 50% by weight.
- Preferred upper limits are 70 and 60 wt .-%. The mentioned upper and lower limits can be combined as desired to areas according to the invention. Further preferred areas according to the invention are specified in subclaim 2.
- Preferred ranges for the pKa of the acids used are -6 to 1, 1.5 or 2, -5 to 1, 1.5 or 2 and -4 to 1, 1.5 or 2.
- the composition according to the invention has a negative pH, preferred are pH values ⁇ -0.1, ⁇ -0.5 and ⁇ -1.
- the selection of sufficiently low volatile acids takes place on the basis of the vapor pressure of the pure acid in a conditioner, which is preferably 80 mbar, 50 mbar, 20 at 20 ° C. mbar, 10 mbar or even 5 mbar.
- a conditioner which is preferably 80 mbar, 50 mbar, 20 at 20 ° C. mbar, 10 mbar or even 5 mbar.
- the vapor pressure of a concentrated acid or a saturated (preferably aqueous) solution of the corresponding acid can be considered, which preferably does not exceed said limits.
- preference is given to using no hydrohalic acids.
- the conditioner may additionally contain thickening agents such as particulate fillers or higher viscosity materials.
- thickeners are, for example, silicic acids, polyethers or polyols and also polyacrylic acids and their copolymers.
- Other additives such as dyes or surfactants (surfactants) may also be included.
- the invention thus relates to a kit for carrying out an infiltration of tooth enamel, which has as constituents a conditioner composition and an infiltrant.
- the infiltrant is preferably a thermosetting (eg photohardenable) resin which can penetrate and seal the lesion after conditioning of the lesion by the conditioner.
- the infiltrant contains at least one resin selected from the group consisting of MMA, methyl methacrylate; EMA, ethyl methacrylate; n-BMA, n-butyl methacrylate; IBMA, isobutyl methacrylate, t-BMA, tert-butyl methacrylate; EHMA, 2-ethylhexyl methacrylate; LMA, lauryl methacrylate; TDMA, tridecyl methacrylate; SMA, stearyl methacrylate; CHMA, cyclohexyl methacrylate; BZMA, benzyl methacrylate; IBXMA, isobornyl methacrylates; MAA, methacrylic acid; HEMA, 2-hydroxyethyl methacrylate; HPMA, 2-hydroxypropyl methacrylate; DMMA, dimethylaminoethyl methacrylate; DEMA, diethylaminoethy
- Further preferred subgroups for the selection of the infiltrant are triethylene glycol dimethacrylate and trimethylolpropane trimethacrylate.
- the kit according to the invention may contain application strips, cleaning strips and / or separating devices.
- the separating device is an instrument with which approximal surfaces of two adjacent teeth can be slightly spaced (for example, approximately 300 ⁇ m).
- Cleaning strips can be provided with a suitable cleaning solution for the preparatory cleaning of dental surfaces to be treated.
- Application strips may be impregnated with the conditioning agent or the infiltrant and thus enable a simple and precise application of these components of the kit to hard-to-reach approximal surfaces of teeth.
- hydroxyapatite [Ca 5 (PO 4 ) 3 OH] x2 (hydroxyapatite platelets) was investigated as a model system for enamel, which consists to about 95% of hydroxyapatite.
- Different conditioner or conditioning solutions can hereby be assessed and classified under reproducible conditions with respect to their etching effect become. The procedure is described in the publication of A. Klocke et al., Dental Materials 19 (2003), 773 described.
- the hydroxyapatite wafers were produced by hydraulic pressing (weighing: 300 mg, pressure: 5000 bar, time: 35 min) of dried (2 h, 60 ° C.) hydroxyapatite (Riedel de Haen) with the IR pressing tool (LOT GmbH). Subsequently, the compacts were so in a plastic (Paladur ®, Heraeus Kulzer GmbH) embedded such that only one surface was uncovered. This surface was treated with sandpaper (grain size: 500 and 1200) in order to obtain as reproducible surfaces as possible and to remove the grinding dust with compressed air. The diameter of the hydroxyapatite surface was 13 mm.
- the hydroxyapatite platelets were immersed in 4 ml of conditioning solution and shaken in the closed test vessel for 2 min on a shaking apparatus (GFL, 100 min -1 ). Subsequently, the hydroxyapatite plates were carefully removed with tweezers from the solution and rinsed thoroughly with water (quality: Hyperpur). The rinse water was returned to the sample vial. The contents of the sample vessel were then transferred to a 100 ml volumetric flask, wherein the sample vessel was rinsed twice with water and the wash water was also collected in the volumetric flask. The volumetric flask was always filled with water up to the 100 ml calibration mark. By atomic absorption spectroscopy (Perkin Elmer), the Ca concentration of this solution was determined.
- Table 1 below lists compositions of the invention as conditioning agents prepared by diluting commercially available acids in distilled water by means of a magnetic stirrer.
- the acids 1 to 4 are comparative examples, the acids 5 to 9 examples according to the invention.
- the last column of Table 1 indicates the calcium concentration obtained for each acid after the experiment described above.
- Table 1 acid pKs (pure acid) Salary [%] Conc. [Mol / l] Ca Conc. [Mg / l] 1.
- compositions according to the invention have a markedly improved etching effect even with respect to 15% strength hydrochloric acid, without having the disadvantages of hydrochloric acid described.
- etching gels were prepared from compositions 1, 5 and 8.
- the solutions were thickened by the addition of 5 wt .-% fumed silica (Aerosil® 200, Degussa) and 0.5 wt .-% sorbitol-based polyether polyol having a hydroxyl number of 500.
- the mixing takes place in a speed mixer (DAC 150 FV , Hauschild).
- DAC 150 FV DAC 150 FV , Hauschild
- the acids used in the embodiments do not form insoluble calcium salts under the conditions of use. This is generally a preferred feature of the invention.
Description
Die Erfindung betrifft ein Kit zur Infiltration von Schmelzläsionen, das eine Zusammensetzung zur Verwendung als Konditioniermittel für das Ätzen von Schmelzläsionen enthält.The invention relates to a kit for the infiltration of enamel lesions containing a composition for use as a conditioner for the etching of enamel lesions.
Karies ist eine weitverbreitete Zivilisationskrankheit. Jede letztendlich zu einer Kavitation führende Karieserkrankung beginnt mit einer Demineralisierung des Zahnschmelzes und wird in diesem Stadium initiale Zahnschmelzkaries genannt. In diesem Stadium ist die Karies zunächst nicht oder lediglich als sogenannte weiße Zahnschmelzläsion sichtbar, führt aber zu einem porösen Bereich des Zahns unterhalb dessen Oberfläche.Caries is a widespread lifestyle disease. Any cavitation-related caries disease begins with demineralization of the enamel and is called initial enamel caries at this stage. At this stage, the caries is initially not visible or only as a so-called white tooth enamel lesion, but leads to a porous area of the tooth below the surface.
Eine solche Schmelzläsion kann grundsätzlich remineralisiert oder mit einem Kunstharz infiltriert werden (
Der Erfindung liegt die Aufgabe zugrunde, ein wirksames und gut lagerfähiges und anwendbares Konditioniermittel für das Ätzen von Schmelzläsionen zu schaffen.The invention has for its object to provide an effective and well storable and applicable conditioning agent for the etching of enamel lesions.
Die Erfindung betrifft somit einen Kit zur Durchführung einer Infiltration von Zahnschmelz, mit den Bestandteilen:
- a) einem Konditionierer für das Ätzen von Schmelzläsionen, der enthält:
- a2) 4 bis 80 Gew.-% wenigstens einer Säure, die einen pKs-Wert von 2 oder weniger aufweist;
- b2) ein protisches Lösungsmittel;
wobei die Säure bei 20°C einen Sättigungsdampfdruck von 120 mbar oder weniger aufweist;
- b) einem Infiltranten.
- a) a conditioner for the etching of enamel lesions, which contains:
- a2) 4 to 80% by weight of at least one acid having a pKa of 2 or less;
- b2) a protic solvent;
wherein the acid has a saturation vapor pressure of 120 mbar or less at 20 ° C;
- b) an infiltrant.
Die Säure mit einem pKs-Wert von 2 oder weniger kann eine anorganische oder organische Säure sein, Mischungen mehrerer Säuren sind ebenfalls möglich. Soweit es sich um eine mehrbasige Säure handelt, muss die erste Dissoziationsstufe aus dem in der Zusammensetzung vorliegenden Zustand der Säure einen pKs-Wert von 2 oder weniger aufweisen. Bevorzugte Obergrenzen für den pKs-Wert sind 1,5 und 1.The acid having a pKa of 2 or less may be an inorganic or organic acid, mixtures of several acids are also possible. In the case of a polybasic acid, the first stage of dissociation from the acidic state of the composition must have a pKa of 2 or less. Preferred upper limits for the pKs value are 1.5 and 1.
Bei dem protischen Lösungsmittel kann es sich insbesondere um Alkohole oder Wasser bzw. Mischungen daraus handeln. Erfindungsgemäß ist vorgesehen, dass die Säure und/oder die komplette Zusammensetzung bei 20°C einen Sättigungsdampfdruck von 120 mbar oder weniger aufweisen. Der Sättigungsdampfdruck ist der Druck der gasförmigen Phase eines Stoffes, wenn Flüssig- und Gasphase sich im Gleichgewicht befinden.The protic solvent may in particular be alcohols or water or mixtures thereof. According to the invention it is provided that the acid and / or the complete composition at 20 ° C have a saturation vapor pressure of 120 mbar or less. The saturation vapor pressure is the pressure of the gaseous phase of a substance when the liquid and gas phases are in equilibrium.
Im Rahmen der Erfindung wird bevorzugt der Partialdampfdruck lediglich der Säure in der Zusammensetzung betrachtet, es kann dann der Dampfdruck des Lösungsmittels außer Acht gelassen werden.In the context of the invention, the partial vapor pressure of only the acid in the composition is preferably considered, and then the vapor pressure of the solvent can be disregarded.
Die Erfindung hat erkannt, dass im Stand der Technik (
Die Erfindung hat erkannt, dass die im Patentanspruch näher definierten Säuren mit einem bestimmten Mindestwert der Säurestärke die remineralisierten Oberflächenschichten natürlicher Schmelzläsionen wirksam erodieren und damit für das Einpenetrieren eines Infiltranten vorbereiten können. Solche pseudointakten Oberflächenschichten einer natürlichen Schmelzläsion sind typischerweise 10 bis 40 µm dick und werden durch eine erfindungsgemäße Zusammensetzung dennoch in handhabbaren Applikationszeiten (beispielsweise etwa 90 bis 120 s) weitgehend vollständig durchdrungen und entfernt.The invention has recognized that the acids defined in more detail in the claim with a certain minimum value of the acid strength can effectively erode the remineralized surface layers of natural enamel lesions and thus prepare for the penetration of an infiltrant. Such pseudointact surface layers of a natural enamel lesion are typically 10 to 40 microns thick and are largely completely penetrated by a composition of the invention in manageable application times (for example, about 90 to 120 s) and completely removed.
Der erfindungsgemäß vorgesehene niedrige Sättigungsdampfdruck stellt sicher, dass es -anders als bei der Verwendung von Salzsäure- nicht zum Entweichen aggressiver Säurebestandteile bei Lagerung oder Anwendung der erfindungsgemäßen Zusammensetzung kommt.The low saturation vapor pressure provided according to the invention ensures that-unlike the use of hydrochloric acid-there is no escape of aggressive acid constituents during storage or use of the composition according to the invention.
Geeignete Säuren sind beispielsweise Fluorsulfonsäure, organische Sulfonsäuren wie bspw. Trifluormethansulfonsäure, Methansulfonsäure, Toluolsulfonsäure, Amidosulfonsäure, Benzolsulfonsäure, Perchlorsäure, Schwefelsäure, Salpetersäure, Trichloressigsäure, Trifluoressigsäure, Pikrinsäure oder Semiquadratsäure. Bevorzugte Säuren sind Methansulfonsäure und p-Toluolsulfonsäure.Suitable acids are, for example, fluorosulfonic acid, organic sulfonic acids, such as, for example, trifluoromethanesulfonic acid, methanesulfonic acid, toluenesulfonic acid, sulfamic acid, benzenesulfonic acid, perchloric acid, sulfuric acid, nitric acid, trichloroacetic acid, trifluoroacetic acid, picric acid or semiqua decarboxylic acid. Preferred acids are methanesulfonic acid and p-toluenesulfonic acid.
Bevorzugte Untergrenzen für den Säuregehalt im Konditioniermittel sind 7 Gew.-%, 10 Gew.-%, 11 Gew.-%, 15 Gew.-%, 20 Gew.-%, 25 Gew.-%, 30 Gew.-%, 40 Gew.-% und 50 Gew.-%. Bevorzugte Obergrenzen sind 70 und 60 Gew.-%. Die genannten Ober- und Untergrenzen können beliebig zu erfindungsgemäßen Bereichen kombiniert werden. Weitere bevorzugte erfindungsgemäße Bereiche sind in Unteranspruch 2 angegeben.Preferred lower limits for the acidity in the conditioning agent are 7% by weight, 10% by weight, 11% by weight, 15% by weight, 20% by weight, 25% by weight, 30% by weight, 40% by weight and 50% by weight. Preferred upper limits are 70 and 60 wt .-%. The mentioned upper and lower limits can be combined as desired to areas according to the invention. Further preferred areas according to the invention are specified in subclaim 2.
Bevorzugte Bereiche für den pKs-Wert der verwendeten Säuren sind -6 bis 1, 1,5 oder 2, -5 bis 1, 1,5 oder 2 und -4 bis 1, 1,5 oder 2. Bevorzugt weist die erfindungsgemäße Zusammensetzung einen negativen pH-Wert auf, bevorzugt sind pH-Werte <-0,1, <-0,5 und <-1.Preferred ranges for the pKa of the acids used are -6 to 1, 1.5 or 2, -5 to 1, 1.5 or 2 and -4 to 1, 1.5 or 2. Preferably, the composition according to the invention has a negative pH, preferred are pH values <-0.1, <-0.5 and <-1.
Die Auswahl hinreichend wenig flüchtiger Säuren erfolgt erfindungsgemäß anhand des Dampfdrucks der reinen Säure in einem Konditionierer, der bevorzugt bei 20°C 80 mbar, 50 mbar, 20 mbar, 10 mbar oder auch 5 mbar nicht übersteigt. Alternativ kann der Dampfdruck einer konzentrierten Säure bzw. einer gesättigten (bevorzugt wässrigen) Lösung der entsprechenden Säure betrachtet werden, der die genannten Grenzen bevorzugt nicht übersteigt. Bevorzugt werden erfindungsgemäß keine Halogenwasserstoffsäuren eingesetzt.According to the invention, the selection of sufficiently low volatile acids takes place on the basis of the vapor pressure of the pure acid in a conditioner, which is preferably 80 mbar, 50 mbar, 20 at 20 ° C. mbar, 10 mbar or even 5 mbar. Alternatively, the vapor pressure of a concentrated acid or a saturated (preferably aqueous) solution of the corresponding acid can be considered, which preferably does not exceed said limits. According to the invention, preference is given to using no hydrohalic acids.
Der Konditionierer kann zusätzlich Verdickungsmittel wie beispielsweise partikuläre Füllstoffe oder höher viskose Stoffe enthalten. Geeignete Verdickungsmittel sind beispielsweise Kieselsäuren, Polyether oder Polyole sowie Polyacrylsäuren und deren Copolymere. Weitere Zusatzstoffe wie beispielsweise Farbstoffe oder grenzflächenaktive Stoffe (Tenside) können ebenfalls enthalten sein.The conditioner may additionally contain thickening agents such as particulate fillers or higher viscosity materials. Suitable thickeners are, for example, silicic acids, polyethers or polyols and also polyacrylic acids and their copolymers. Other additives such as dyes or surfactants (surfactants) may also be included.
Gegenstand der Erfindung ist somit ein Kit zur Durchführung einer Infiltration von Zahnschmelz, der als Bestandteile eine Konditioniererzusammensetzung sowie einen Infiltranten aufweist. Bei dem Infiltranten handelt es sich bevorzugt um ein härtbares (beispielsweise lichthärtbares) Kunstharz, das nach der Vorbereitung der Läsion durch den Konditionierer in diese Läsion einpenetrieren und diese versiegeln kann.The invention thus relates to a kit for carrying out an infiltration of tooth enamel, which has as constituents a conditioner composition and an infiltrant. The infiltrant is preferably a thermosetting (eg photohardenable) resin which can penetrate and seal the lesion after conditioning of the lesion by the conditioner.
Bevorzugt weist in diesem Kit der verwendete Infiltrant einen Penetrationskoeffizienten von mehr als 50 cm/s auf. Der Penetrationskoeffizient errechnet sich nach der nachfolgend aufgeführten, aus der sogenannten Washburn-Gleichung ableitbaren Gleichung:
- PC:
- Penetrationskoeffizient
- γ:
- Oberflächenspannung des Infiltranten an der Grenzfläche zur Luft
- θ:
- Kontaktwinkel des Infiltranten an der Grenzfläche zur Schmelz
- η:
- dynamische Viskosität des Infiltranten
- PC:
- penetration coefficient
- γ:
- Surface tension of the infiltrant at the interface with the air
- θ:
- Contact angle of the infiltrant at the interface to the enamel
- η:
- dynamic viscosity of the infiltrant
Weitere Angaben zur Bestimmung des Penetrationskoeffizienten einschließlich Literaturhinweisen finden sich in der bereits genannten
Bevorzugt enthält der Infiltrant wenigstens ein Harz ausgewählt aus der Gruppe bestehend aus MMA, Methylmethacrylat; EMA, Ethylmethacrylat; n-BMA, n-Butylmethacrylat; IBMA, Isobutylmethacrylat, t-BMA, tert-Butylmethacrylat; EHMA, 2-Ethylhexylmethacrylat; LMA, Laurylmethacrylat; TDMA, Tridecylmethacrylat; SMA, Stearylmethacrylat; CHMA, Cyclohexylmethacrylat; BZMA, Benzylmethacrylat; IBXMA, Isobornylmethacrylate; MAA, Methacrylsäure; HEMA, 2-Hydroxyethylmethacrylat; HPMA, 2-Hydroxypropylmethacrylat; DMMA, Dimethylaminoethylmethacrylat; DEMA, Diethylaminoethylmethacrylat; GMA, Glycidylmethacrylat; THFMA, Tetrahydrofurfurylmethacrylat; AMA, Allylmethacrylat; EGDMA, Ethylenglycoldimethacrylat; 3EGDMA, Triethylenglycoldimethacrylat; 4EGDMA, Tetraethylenglycoldimethacrylat; BDMA, 1,3-Butylenglycoldimethacrylat; HDDMA, 1,6-Hexandioldimethacrylat; ETMA, Ethoxyethylmethacrylat; 3FM, Trifluorethylmethacrylat; 8FM, Octafluorpentylmethacrylat; AIB, Isobutylacrylat; TBA, tert-Butylacrylat; LA, Laurylacrylat; CEA, Cetylacrylat; STA, Stearylacrylat; CHA, Cyclohexylacrylat; BZA, Benzylacrylat; IBXA, Isobornylacrylat; 2-MTA, 2-Methoxyethylacrylat; ETA, 2-Ethoxyethylacrylat; EETA, Ethoxyethoxyethylacrylat; PEA, 2-Phenoxyethylacrylat; THFA, Tetrahydrofurfurylacrylat; HEA, 2-Hydroxyethylacrylat; HPA, 2-Hydroxypropylacrylat; 4HBA, 4-Hydroxybutylacrylat; DMA, Dimethylaminoethylacrylat; 1,4-Butylendioldiacrylat; 4EDA, Tetraethylenglycoldiacrylat; NDDA, 1,9- Nonandioldiacrylat; 3F, Trifluorethylacrylat; 17F, Heptadecafluorodecylacrylat; 2-PEA, 2-Phenoxyethylacrylat; TBCH, 4-tert-butylcyclohexylacrylat; DCPA, Dihydrodicyclopentadienylacrylat; EHA, 2-Ethylhexylacrylat; 3EGMA, Triethylenglycolmonomethacrylat; DEGDMA, Diethylenglycoldimethacrylat; PDDMA, 1,5-Pentandioldimethacrylat; BDDMA, 1,4-Butandioldimethacrylat; PRDMA, 1,3-Propandioldimethacrylat (alle vorstehenden Harze besitzen eine Viskosität < 30 mPas) oder aus der Gruppe bestehend aus DDDMA, 1,10-Decandioldimethacrylat; PEG400DA, Polyethylenglycol 400 Diacrylat, TMPTMA, Trimethylolpropantrimethacrylat, TMPTA, Trimethylolpropantriacrylat; DTMPTA; Di-Trimethylolpropantetraacrylat; DiPENTA, Di-Pentaerythritolpentaacrylat; PEG400DMA, Polyethylenglycol 400 Dimethacrylat, PEG300DA, Polyethylenglycol 300 Diacrylat, PEG300DMA, Polyethylenglycol 300 Dimethacrylat, BPA(EO)10DMA, Ethoxyliertes (10) Bisphenol-A-Dimethacrylat; BPA(EO)30DMA, Ethoxyliertes (30) Bisphenol-A-Dimethacrylat; PEG200DA, Polyethylenglycol 200 Diacrylat, PEG600DA, Polyethy-lenglycol 600 Diacrylat; NPG(PO)2DA Propoxyliertes (2) Neopentylglycol Diacrylat; BPA(EO)2DA, Ethoxyliertes (4) Bisphenol-A-Diacrylat; GPTA; propoxyliertes Glyceryltriacrylat; BPA(PO)2DMA, Propoxyliertes (2) Bisphenol-A-Dimethacrylat; DPEHA, Dipentaerythritolhexaacrylat; Bis-GMA, 2,2-bis[4-(2-Hydroxy-3-Methacryloxypropoxy)phenyl]propan; und UDMA, 1,6-bis(Methacryloxy-2-Ethoxycarbonylamino)-2,4,4-trimethylhexan; (alle vorstehenden Harze besitzen eine Viskosität > 30 mPas).Preferably, the infiltrant contains at least one resin selected from the group consisting of MMA, methyl methacrylate; EMA, ethyl methacrylate; n-BMA, n-butyl methacrylate; IBMA, isobutyl methacrylate, t-BMA, tert-butyl methacrylate; EHMA, 2-ethylhexyl methacrylate; LMA, lauryl methacrylate; TDMA, tridecyl methacrylate; SMA, stearyl methacrylate; CHMA, cyclohexyl methacrylate; BZMA, benzyl methacrylate; IBXMA, isobornyl methacrylates; MAA, methacrylic acid; HEMA, 2-hydroxyethyl methacrylate; HPMA, 2-hydroxypropyl methacrylate; DMMA, dimethylaminoethyl methacrylate; DEMA, diethylaminoethyl methacrylate; GMA, glycidyl methacrylate; THFMA, tetrahydrofurfuryl methacrylate; AMA, allyl methacrylate; EGDMA, ethylene glycol dimethacrylate; 3EGDMA, triethylene glycol dimethacrylate; 4EGDMA, tetraethylene glycol dimethacrylate; BDMA, 1,3-butylene glycol dimethacrylate; HDDMA, 1,6-hexanediol dimethacrylate; ETMA, ethoxyethyl methacrylate; 3FM, trifluoroethyl methacrylate; 8FM, octafluoropentyl methacrylate; AIB, isobutyl acrylate; TBA, tert-butyl acrylate; LA, lauryl acrylate; CEA, cetyl acrylate; STA, stearyl acrylate; CHA, cyclohexyl acrylate; BZA, benzyl acrylate; IBXA, isobornyl acrylate; 2-MTA, 2-methoxyethyl acrylate; ETA, 2-ethoxyethyl acrylate; EETA, ethoxyethoxyethyl acrylate; PEA, 2-phenoxyethyl acrylate; THFA, tetrahydrofurfuryl acrylate; HEA, 2-hydroxyethyl acrylate; HPA, 2-hydroxypropyl acrylate; 4HBA, 4-hydroxybutyl acrylate; DMA, dimethylaminoethyl acrylate; 1,4-Butylendioldiacrylat; 4EDA, tetraethylene glycol diacrylate; NDDA, 1,9-nonanediol diacrylate; 3F, trifluoroethyl acrylate; 17F, heptadecafluorodecyl acrylate; 2-PEA, 2-phenoxyethyl acrylate; TBCH, 4-tert-butylcyclohexyl acrylate; DCPA, dihydrodicyclopentadienyl acrylate; EHA, 2-ethylhexyl acrylate; 3EGMA, triethylene glycol monomethacrylate; DEGDMA, diethylene glycol dimethacrylate; PDDMA, 1,5-pentanediol dimethacrylate; BDDMA, 1,4-butanediol dimethacrylate; PRDMA, 1,3-propanediol dimethacrylate (all the above resins have a viscosity <30 mPas) or from the group consisting of DDDMA, 1,10-decanediol dimethacrylate; PEG400DA, polyethylene glycol 400 diacrylate, TMPTMA, trimethylolpropane trimethacrylate, TMPTA, trimethylolpropane triacrylate; DTMPTA; Di-trimethylolpropane; DiPENTA, di-pentaerythritol pentaacrylate; PEG400DMA, polyethylene glycol 400 dimethacrylate, PEG300DA, polyethylene glycol 300 diacrylate, PEG300DMA, polyethylene glycol 300 dimethacrylate, BPA (EO) 10DMA, ethoxylated (10) bisphenol A dimethacrylate; BPA (EO) 30DMA, ethoxylated (30) bisphenol A dimethacrylate; PEG200DA, polyethylene glycol 200 diacrylate, PEG600DA, polyethylene glycol 600 diacrylate; NPG (PO) 2DA Propoxylated (2) neopentyl glycol diacrylate; BPA (EO) 2DA, ethoxylated (4) bisphenol A diacrylate; GPTA; propoxylated glyceryl triacrylate; BPA (PO) 2DMA, propoxylated (2) bisphenol A dimethacrylate; DPEHA, dipentaerythritol hexaacrylate; Bis-GMA, 2,2-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane; and UDMA, 1,6-bis (methacryloxy-2-ethoxycarbonylamino) -2,4,4-trimethylhexane; (All the above resins have a viscosity> 30 mPas).
Weitere bevorzugte Untergruppen für die Auswahl des Infiltranten sind Triethylenglycoldimethacrylat und Trimethylolpropantrimethacrylat.Further preferred subgroups for the selection of the infiltrant are triethylene glycol dimethacrylate and trimethylolpropane trimethacrylate.
Der erfindungsgemäße Kit kann Applikationsstreifen, Reinigungsstreifen und/oder Trenneinrichtungen enthalten. Bei der Trenneinrichtung handelt es sich um ein Instrument, mit dem sich Approximalflächen zweier benachbarter Zähne geringfügig (beispielsweise ca. 300 µm) beabstanden lassen. Reinigungsstreifen können mit einer entsprechenden Reinigungslösung zur vorbereitenden Reinigung zu behandelnder Dentalflächen versehen sein. Applikationsstreifen können mit dem Konditioniermittel bzw. dem Infiltranten getränkt sein und so ein einfaches und präzises Applizieren dieser Bestandteile des Kits auch auf schwer zugängliche Approximalflächen von Zähnen ermöglichen.The kit according to the invention may contain application strips, cleaning strips and / or separating devices. The separating device is an instrument with which approximal surfaces of two adjacent teeth can be slightly spaced (for example, approximately 300 μm). Cleaning strips can be provided with a suitable cleaning solution for the preparatory cleaning of dental surfaces to be treated. Application strips may be impregnated with the conditioning agent or the infiltrant and thus enable a simple and precise application of these components of the kit to hard-to-reach approximal surfaces of teeth.
In den nachfolgenden Ausführungsbeispielen und Vergleichsbeispielen wird die Eignung verschiedener Konditioniermittel zum Erodieren bzw. Demineralisieren von remineralisierten Oberflächenschichten natürlicher Schmelzläsionen an einem Modellsystem geprüft.In the following exemplary embodiments and comparative examples, the suitability of various conditioning agents for eroding or demineralizing remineralized surface layers of natural enamel lesions on a model system is examined.
Dabei wurde die Ätzwirkung auf Hydroxylapatit [Ca5(PO4)3OH]x2 (Hydroxylapatit-Plättchen) als Modellsystem für Schmelz, der zu etwa 95 % aus Hydroxylapatit besteht, untersucht. Unterschiedliche Konditioniermittel- oder Konditionierlösungen können hiermit unter reproduzierbaren Bedingungen bzgl. ihrer Ätzwirkung eingeschätzt und klassifiziert werden. Das Verfahren wird in der Publikation von
Die Hydroxylapatit-Plättchen wurden durch hydraulisches Pressen (Einwaage: 300mg; Druck: 5000 bar; Zeit: 35min) von getrocknetem (2h, 60°C) Hydroxylapatit (Riedel de Haen) mit dem IR-Presswerkzeug (Firma LOT GmbH) hergestellt. Anschließend wurden die Presslinge so in einen Kunststoff (Paladur®, Heraeus Kulzer GmbH) eingebettet, dass nur eine Fläche unbedeckt blieb. Diese Fläche wurde mit Schleifpapier (Körnung: 500 und 1200) bearbeitet, um möglichst reproduzierbare Oberflächen zu erhalten und mit Pressluft vom Schleifstaub befreit. Der Durchmesser der Hydroxylapatitfläche betrug 13 mm.The hydroxyapatite wafers were produced by hydraulic pressing (weighing: 300 mg, pressure: 5000 bar, time: 35 min) of dried (2 h, 60 ° C.) hydroxyapatite (Riedel de Haen) with the IR pressing tool (LOT GmbH). Subsequently, the compacts were so in a plastic (Paladur ®, Heraeus Kulzer GmbH) embedded such that only one surface was uncovered. This surface was treated with sandpaper (grain size: 500 and 1200) in order to obtain as reproducible surfaces as possible and to remove the grinding dust with compressed air. The diameter of the hydroxyapatite surface was 13 mm.
Für die Ätzversuche wurden die Hydroxylapatit-Plättchen in 4 ml Konditionierlösung getaucht und im verschlossenen Probegefäß für 2 min auf einem Schüttelapparat (GFL; 100 min-1) gerüttelt. Anschließend wurden die Hydroxylapatit-Plättchen vorsichtig mit einer Pinzette aus der Lösung genommen und mit Wasser (Qualität: Hyperpur) gründlich abgespült. Das Spülwasser wurde zurück in das Probegefäß gegeben. Der Inhalt des Probengefäßes wurde anschließend in einen 100 ml Meßkolben überführt, wobei das Probegefäß noch 2 mal mit Wasser ausgespült und das Waschwasser ebenfalls im Meßkolben aufgefangen wurde. Der Meßkolben wurde stets bis zur 100 ml-Eichmarke mit Wasser aufgefüllt. Mittels Atomabsorptionsspektroskopie (Perkin Elmer) wurde die Ca-Konzentration dieser Lösung bestimmt.For the etching experiments, the hydroxyapatite platelets were immersed in 4 ml of conditioning solution and shaken in the closed test vessel for 2 min on a shaking apparatus (GFL, 100 min -1 ). Subsequently, the hydroxyapatite plates were carefully removed with tweezers from the solution and rinsed thoroughly with water (quality: Hyperpur). The rinse water was returned to the sample vial. The contents of the sample vessel were then transferred to a 100 ml volumetric flask, wherein the sample vessel was rinsed twice with water and the wash water was also collected in the volumetric flask. The volumetric flask was always filled with water up to the 100 ml calibration mark. By atomic absorption spectroscopy (Perkin Elmer), the Ca concentration of this solution was determined.
In der nachfolgenden Tabelle 1 sind erfindungsgemäße Zusammensetzungen als Konditioniermittel aufgeführt, die durch Verdünnen kommerziell erhältlicher Säuren in destilliertem Wasser mittels Magnetrührer hergestellt wurden. Die Säuren 1 bis 4 sind Vergleichsbeispiele, die Säuren 5 bis 9 erfindungsgemäße Beispiele. Die letzte Spalte der Tabelle 1 gibt die nach dem oben beschriebenen Versuch erhaltene Calciumkonzentration für die jeweilige Säure an.
Die Tabelle zeigt, dass die erfindungsgemäßen Zusammensetzungen selbst gegenüber 15%iger Salzsäure eine deutlich verbesserte Ätzwirkung aufweisen, ohne die beschriebenen Nachteile der Salzsäure aufzuweisen.The table shows that the compositions according to the invention have a markedly improved etching effect even with respect to 15% strength hydrochloric acid, without having the disadvantages of hydrochloric acid described.
Zur Überprüfung der Lagerstabilität wurden aus den Zusammensetzungen 1, 5 und 8 Ätzgele hergestellt. Zu diesem Zweck wurden die Lösungen angedickt durch Zusatz von 5 Gew.-% pyrogener Kieselsäure (Aerosil® 200, Degussa) und 0,5 Gew.-% sorbitolbasiertes Polyetherpolyol mit einer Hydroxylzahl von 500. Die Vermischung erfolgt in einem Speedmixer (DAC 150 FV, Fa. Hauschild). Diese gelartigen Konditioniermittel wurden in übliche dentale Applikationsspritzen für Gele (Etching Gel, DMG) eingeführt und sieben Tage bei 60°C gelagert.To test the storage stability, etching gels were prepared from compositions 1, 5 and 8. For this purpose, the solutions were thickened by the addition of 5 wt .-% fumed silica (Aerosil® 200, Degussa) and 0.5 wt .-% sorbitol-based polyether polyol having a hydroxyl number of 500. The mixing takes place in a speed mixer (DAC 150 FV , Hauschild). These gel-like conditioning agents were introduced into conventional dental gel application gels (Etching Gel, DMG) and stored at 60 ° C. for seven days.
Zur Bestimmung der Lagerstabilität wurde die Säurekonzentration vor und nach der Lagerung gemessen. Die Ergebnisse sind in der nachfolgenden Tabelle 2 aufgeführt.
Man erkennt, dass die Säurekonzentration des Salzsäuregels durch Entweichen des HCl-Gases abgenommen hat, während die Konzentration der übrigen, kaum flüchtigen Säuren durch Verflüchtigung eines geringen Teils des als Lösungsmittel verwendeten Wasser geringfügig zugenommen hat.It can be seen that the acid concentration of the hydrochloric acid gel has decreased by the escape of the HCl gas, while the concentration of the remaining, hardly volatile acids has increased slightly by volatilization of a small portion of the water used as solvent.
Die bei den Ausführungsbeispielen verwendeten Säuren bilden unter den Bedingungen der Anwendung keine unlöslichen Calciumsalze. Dies ist generell ein bevorzugtes Merkmal der Erfindung.The acids used in the embodiments do not form insoluble calcium salts under the conditions of use. This is generally a preferred feature of the invention.
Claims (13)
- A kit for carrying out an infiltration of dental enamel, with the constituents:a) a conditioner for etching enamel lesions which comprisesa1) 4 to 80% by weight of at least one acid which has a pKa of 2 or less;a2) a protic solvent;
wherein the acid having a saturation vapor pressure at 20° C of 120 mbar or less, for use as conditioning agent for etching enamel lesions;b) an infiltrant. - Kit according to claim 1, characterised in that the acid content of the conditioner is from 11 to 80% by weight, preferably 15 to 80% by weight, more preferably 20 to 70% by weight, more preferably 25 to 60% by weight.
- Kit according to either claim 1 or claim2, characterised in that the pKa of the acid is from -6 to 1, preferably -5 to 1, more preferably -4 to 1.
- Kit according to any of claims 1 to 3, characterised in that the protic solvent is selected from the group consisting of water and alcohols.
- Kit according to any of claims 1 to 4, characterised in that the partial vapor pressure of the acid in the composition at 20° C is 80 mbar or less, preferably 50 mbar or less, more preferably 20 mbar or less, more preferably 10 mbar or less.
- Kit according to any of claims 1 to 5, characterised in that the conditioner additionally comprises thickeners.
- Kit according to claim 6, characterised in that the thickeners are selected from the group consisting of particulate fillers and polyethers.
- Kit according to any of claims 1 to 7, characterised in that the infiltrant has a penetration coefficient PC of >50 cm/s.
- Kit according to claim 8, characterised in that the infiltrant comprises at least one resin selected from the group consisting of MMA, methyl methacrylate; EMA, ethyl methacrylate; n-BMA, n-butyl methacrylate; IBMA, isobutyl methacrylate, t-BMA, tert-butyl methacrylate; EHMA, 2-ethylhexyl methacrylate; LMA, lauryl methacrylate; TDMA, tridecyl methacrylate; SMA, stearyl methacrylate; CHMA, cyclohexyl methacrylate; BZMA, benzyl methacrylate; IBXMA, isobornyl methacrylate; MAA, methacrylic acid; HEMA, 2-hydroxyethyl methacrylate; HPMA, 2-hydroxypropyl methacrylate; DMMA, dimethylaminoethyl methacrylate; DEMA, diethylaminoethyl methacrylate; GMA, glycidyl methacrylate; THFMA, tetrahydrofurfuryl methacrylate; AMA, allyl methacrylate; EGDMA, ethylene glycol dimethacrylate; 3EGDMA, triethylene glycol dimethacrylate; 4EGDMA, tetraethylene glycol dimethacrylate; BDMA, 1,3-butylene glycol dimethacrylate; HDDMA, 1,6-hexanediol dimethacrylate; ETMA, ethoxyethyl methacrylate; 3FM, trifluoroethyl methacrylate; 8FM, octafluoropentyl methacrylate; AIB, isobutyl acrylate; TBA, tert-butyl acrylate; LA, lauryl acrylate; CEA, cetyl acrylate; STA, stearyl acrylate; CHA, cyclohexyl acrylate; BZA, benzyl acrylate; IBXA, isobornyl acrylate; 2-MTA, 2-methoxyethyl acrylate; ETA, 2-ethoxyethyl acrylate; EETA, ethoxyethoxyethyl acrylate; PEA, 2-phenoxyethyl acrylate; THFA, tetrahydrofurfuryl acrylate; HEA, 2-hydroxyethyl acrylate; HPA, 2-hydroxypropyl acrylate; 4HBA, 4-hydroxybutyl acrylate; DMA, dimethylaminoethyl acrylate; 1,4-butylenediol diacrylate; 4EDA, tetraethylene glycol diacrylate; NDDA, 1,9-nonanediol diacrylate; 3F, trifluoroethyl acrylate; 17F, heptadecafluorodecyl acrylate; 2-PEA, 2-phenoxyethyl acrylate; TBCH, 4-tert-butylcyclohexyl acrylate; DCPA, dihydrodicyclopentadienyl acrylate; EHA, 2-ethylhexyl acrylate; 3EGMA, triethylene glycol monomethacrylate; DEGDMA, diethylene glycol dimethacrylate; PDDMA, 1,5-pentanediol dimethacrylate; BDDMA, 1,4-butanediol dimethacrylate; PRDMA, 1,3-propanediol dimethacrylate; DDDMA, 1,10-decanediol dimethacrylate; PEG400DA, polyethylene glycol 400 diacrylate, TMPTMA, trimethylolpropane trimethacrylate, TMPTA, trimethylolpropane triacrylate; DTMPTA; di-trimethylolpropane tetraacrylate; DiPENTA, di-pentaerythritol pentaacrylate; PEG400DMA, polyethylene glycol 400 dimethacrylate, PEG300DA, polyethylene glycol 300 diacrylate, PEG300DMA, polyethylene glycol 300 dimethacrylate, BPA(EO)10DMA, ethoxylated (10) bisphenol A dimethacrylate; BPA(EO)30DMA, ethoxylated (30) bisphenol A dimethacrylate; PEG200DA, polyethylene glycol 200 diacrylate, PEG600DA, polyethylene glycol 600 diacrylate; NPG(PO)2DA propoxylated (2) neopentyl glycol diacrylate; BPA(EO)2DA, ethoxylated (4) bisphenol A diacrylate; GPTA; propoxylated glyceryl triacrylate; DMTCDDA, dimethylol tricyclo[5.2.1.0<2,6>]decane dimethacrylate; BPA(PO)2DMA, propoxylated (2) bisphenol A dimethacrylate; DPEHA, dipentaerythritol hexaacrylate; bis-GMA, 2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl]propane; and UDMA, 1,6-bis(methacryloxy-2-ethoxycarbonylamino)-2,4,4-trimethylhexane.
- Kit according to any of claims 8 to 9, characterised in that the infiltrant comprises at least one resin selected from the group consisting of TEGDMA, triethylene glycol dimethacrylate; and TMPTMA, trimethylolpropane trimethacrylate.
- Kit according to any of claims 8 to 10, characterised in that it comprises at least one application strip and/or cleaning strip and/or a separator.
- Kit according to claim 11, characterised in that it comprises an application strip provided with a conditioner.
- Kit according to either claim 11 or claim 12, characterised in that it comprises an application strip provided with an infiltrant.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08007195.4A EP2108356B1 (en) | 2008-04-11 | 2008-04-11 | Conditioning agent for the etching of enamel lesions |
PCT/EP2009/002310 WO2009124671A1 (en) | 2008-04-11 | 2009-03-30 | Conditioning agent for the corrosion of enamel lesions |
BRPI0909805A BRPI0909805A2 (en) | 2008-04-11 | 2009-03-30 | conditioning agent for corrosion of enamel lesions |
US12/422,058 US20090256108A1 (en) | 2008-04-11 | 2009-04-10 | Conditioning agent for etching enamel lesions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP08007195.4A EP2108356B1 (en) | 2008-04-11 | 2008-04-11 | Conditioning agent for the etching of enamel lesions |
Publications (2)
Publication Number | Publication Date |
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EP2108356A1 EP2108356A1 (en) | 2009-10-14 |
EP2108356B1 true EP2108356B1 (en) | 2017-01-25 |
Family
ID=39865410
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08007195.4A Active EP2108356B1 (en) | 2008-04-11 | 2008-04-11 | Conditioning agent for the etching of enamel lesions |
Country Status (4)
Country | Link |
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US (1) | US20090256108A1 (en) |
EP (1) | EP2108356B1 (en) |
BR (1) | BRPI0909805A2 (en) |
WO (1) | WO2009124671A1 (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2145613A1 (en) * | 2008-07-02 | 2010-01-20 | Ernst Mühlbauer GmbH & Co.KG | Infiltrant for dental application |
DE202009016522U1 (en) | 2009-11-24 | 2010-03-04 | Ernst Mühlbauer Gmbh & Co. Kg | Infiltrant for the treatment of an enamel lesion |
DE202010003032U1 (en) * | 2010-02-17 | 2011-08-12 | Ernst Mühlbauer Gmbh & Co. Kg | Infiltration solution for the treatment of an enamel lesion |
DE202012002072U1 (en) | 2012-03-01 | 2013-06-03 | Ernst Mühlbauer Gmbh & Co. Kg | Applicator for occlusal surfaces |
US9682018B2 (en) * | 2014-03-13 | 2017-06-20 | Steven Sadowsky | Denture tooth and material |
DE102021128685A1 (en) | 2021-11-04 | 2023-05-04 | Voco Gmbh | Highly effective, silica-free, storage-stable dental etching gel |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4348381A (en) * | 1981-05-06 | 1982-09-07 | Colgate-Palmolive Company | Dental remineralization composition |
US6036944A (en) * | 1995-08-08 | 2000-03-14 | Enamelon, Inc. | Processes for the remineralization and mineralization of teeth |
CA2310818A1 (en) * | 1998-08-10 | 2000-02-24 | Michail Lytinas | Dental treatment methods |
US6312667B1 (en) * | 1998-11-12 | 2001-11-06 | 3M Innovative Properties Company | Methods of etching hard tissue in the oral environment |
WO2003051316A1 (en) * | 2001-12-18 | 2003-06-26 | John Kanca, Iii | Device for dental applications |
US8686063B2 (en) | 2005-01-21 | 2014-04-01 | Charité—Universitätsmedizin Berlin | Method of infiltrating enamel lesions |
-
2008
- 2008-04-11 EP EP08007195.4A patent/EP2108356B1/en active Active
-
2009
- 2009-03-30 BR BRPI0909805A patent/BRPI0909805A2/en not_active Application Discontinuation
- 2009-03-30 WO PCT/EP2009/002310 patent/WO2009124671A1/en active Application Filing
- 2009-04-10 US US12/422,058 patent/US20090256108A1/en not_active Abandoned
Non-Patent Citations (1)
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None * |
Also Published As
Publication number | Publication date |
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EP2108356A1 (en) | 2009-10-14 |
BRPI0909805A2 (en) | 2015-10-06 |
WO2009124671A1 (en) | 2009-10-15 |
US20090256108A1 (en) | 2009-10-15 |
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